JPS6363652A - Production of n-(2-chloro-4-nitrophenyl)-3-trifluoromethylbenzenesulfonamides - Google Patents
Production of n-(2-chloro-4-nitrophenyl)-3-trifluoromethylbenzenesulfonamidesInfo
- Publication number
- JPS6363652A JPS6363652A JP20799086A JP20799086A JPS6363652A JP S6363652 A JPS6363652 A JP S6363652A JP 20799086 A JP20799086 A JP 20799086A JP 20799086 A JP20799086 A JP 20799086A JP S6363652 A JPS6363652 A JP S6363652A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- chloro
- reaction
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- -1 N-(2-chlorophenyl)-3- trifluoromethylbenzenesulfonamide compound Chemical class 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 9
- 238000006396 nitration reaction Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 4
- ZUTVRDMZQSHCID-UHFFFAOYSA-N 3-(trifluoromethyl)benzenesulfonamide Chemical class NS(=O)(=O)C1=CC=CC(C(F)(F)F)=C1 ZUTVRDMZQSHCID-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 5
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003931 anilides Chemical group 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000000802 nitrating effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SSULGNXFUGLULI-UHFFFAOYSA-N 4-chloro-3-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC(S(Cl)(=O)=O)=CC=C1Cl SSULGNXFUGLULI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- LOCWBQIWHWIRGN-UHFFFAOYSA-N 2-chloro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Cl LOCWBQIWHWIRGN-UHFFFAOYSA-N 0.000 description 1
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-UHFFFAOYSA-N 0.000 description 1
- KWIXNFOTNVKIGM-UHFFFAOYSA-N 2-chloro-5-nitroaniline Chemical compound NC1=CC([N+]([O-])=O)=CC=C1Cl KWIXNFOTNVKIGM-UHFFFAOYSA-N 0.000 description 1
- ONCAZCNPWWQQMW-UHFFFAOYSA-N 3-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=CC(S(Cl)(=O)=O)=C1 ONCAZCNPWWQQMW-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、式（ｎ）で示される新規のＮ−（２−クロロ
−４−ニトロフェニル）−３−トリフロロベンゼンスル
ホンアミド類
入
〔式（ｎ）中、ＸおよびＹはそれぞれ水素原子または塩
素原子を表わす。〕
の製造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention provides novel N-(2-chloro-4-nitrophenyl)-3-trifluorobenzenesulfonamides represented by formula (n) [ In formula (n), X and Y each represent a hydrogen atom or a chlorine atom. ] Regarding the manufacturing method.
さらに詳しくは、式（ｎ）化合物に相応する弐λ
〔式中、ＸＳＹは式（ｎ）中のｘ、 ｙと同じである〕
で示されるＮ−（２−クロロフェニル）−３−トリフロ
ロメチルベンゼンスルホンアミド類をニトロ化して、式
（ｎ）化合物を得る方法に関する。More specifically, 2λ corresponding to the compound of formula (n) [wherein XSY is the same as x and y in formula (n)]
The present invention relates to a method for obtaining a compound of formula (n) by nitrating N-(2-chlorophenyl)-3-trifluoromethylbenzenesulfonamides represented by formula (n).
スルホンアミド類を有するベンゼン系化合物は殺菌剤な
どの農薬として従来より知られている有用な化合物であ
る。Benzene compounds containing sulfonamides are useful compounds that have been known as pesticides such as fungicides.
特開昭５８−２１９１５９号公報には下式〔式中、Ｒ１
、Ｒ２はそれぞれ水素原子、またはメチル基を示し、Ｘ
はメチル基、ハロゲン原子、またはニトロ基を示し、ｎ
は１〜３の整数を示す。ただし、Ｒ１がメチル基、Ｒ２
が水素原子、Ｘが２−クロル−４−二トロ基で表わされ
る化合物、及びＲ１と馬が同時に水素原子で、Ｘが４−
クロルと３，４−ジクロルである化合物を除く。〕で表
わされる３−ニトロベンゼンスルホンアミド系化合物が
提案されており、この化合物は殺菌効果がある記載がな
されている。JP-A-58-219159 discloses the following formula [where R1
, R2 each represent a hydrogen atom or a methyl group, and
represents a methyl group, a halogen atom, or a nitro group, and n
represents an integer from 1 to 3. However, R1 is a methyl group, R2
is a hydrogen atom, X is a 2-chloro-4-nitro group, and R1 and R are both hydrogen atoms, and X is a 4-
Excludes compounds that are chloro and 3,4-dichlor. A 3-nitrobenzenesulfonamide compound represented by the following has been proposed, and this compound is described as having a bactericidal effect.
さらに、本発明と同じ出願人は、上記特開昭５８−２１
９１５９号公報に開示された化合物よりも、より殺菌活
性の大きい化合物である、前記式（ＩＩ）で示されるＮ
−（２−クロロ−４−ニトロフェニル）−３−トリフロ
ロベンゼンスルホンアミド類化合物を見出・し先に出願
した。（特願昭６Ｏ−３６ｓ３２）
〔発明が解決しようとする問題点〕
本発明者らは、式（ｎ）化合物の工業的製造法を確立す
べく、その有利な方法を鋭意検討した。Furthermore, the same applicant as the present invention is
N represented by the above formula (II), which is a compound with greater bactericidal activity than the compound disclosed in Publication No. 9159.
-(2-chloro-4-nitrophenyl)-3-trifluorobenzenesulfonamide compounds were discovered and filed earlier. (Patent Application No. 6O-36S32) [Problems to be Solved by the Invention] In order to establish an industrial method for producing the compound of formula (n), the present inventors have intensively studied advantageous methods thereof.
前記特開昭５８−２１９１５９号公報には、例エバＮ−
（２−クロル−５−ニトロフエニ／ｌ、）−３−を得る
ため、トルエン溶媒中で、２−クロル−５−ニトロアニ
リンと等モルの３−ニトロ−４−メチルベンゼンスルホ
ンクロリドとを、等モル量のピリジンの存在下、還流下
にかきまぜながら縮合反応を実施する記載がある。In the above-mentioned Japanese Patent Application Laid-Open No. 58-219159, there is
In order to obtain (2-chloro-5-nitropheni/l,)-3-, 2-chloro-5-nitroaniline and equimolar amounts of 3-nitro-4-methylbenzenesulfone chloride were mixed in a toluene solvent, etc. There is a description of carrying out the condensation reaction in the presence of a molar amount of pyridine while stirring under reflux.
しかしながら目的生成物の収率はせいぜい５０数％であ
り、該方法に準じて本発明に係る式（ｎ）化合物の製造
方法に適用した場合も殆んど同程度の収率しか得ること
はできなかった。However, the yield of the target product is only a few 50% at most, and even if this method is applied to the method for producing the compound of formula (n) according to the present invention, it is only possible to obtain almost the same yield. There wasn't.
このように本発明において目的生成物が高収率で得られ
ない原因の一つは、反応基質の片方にニトロ基を有する
アニリン類を縮合に用いるためと推定される。One of the reasons why the desired product cannot be obtained in high yield in the present invention is presumed to be that anilines having a nitro group on one of the reaction substrates are used for condensation.
事実、本発明者の縮合反応における実験によれば、例え
ば片方の反応基質に３−トリフロロメチル−４−クロロ
ベンゼンスルホクロリドを選び、これに２−り四ロー４
−ニトロアニリンまたは２−クロロアニリンとを夫々縮
合反応させた場合、縮合反応生成物の収率には約１０％
近くもひらきがあり、あきらかにニトロ基で核置換され
ていない後者を反応に用いたほうが有利であることがわ
かった。In fact, according to the inventor's experiments in condensation reactions, for example, 3-trifluoromethyl-4-chlorobenzenesulfochloride was selected as one of the reaction substrates, and 2-trifluoro-4
- When condensation reactions are carried out with nitroaniline or 2-chloroaniline, the yield of the condensation reaction product is approximately 10%.
There was also an opening nearby, and it was found that it was more advantageous to use the latter, which was not clearly substituted with a nitro group, in the reaction.
その上、２−クロロ−４−ニトロアニリンを用いる場合
はその製造は通常、ジクロルベンゼンを出発原料とし、
これのニトロ化、アンモノリシスと工程が長いため高価
な上に高純度のものが得がたいので、原料的にも不利で
ある。Moreover, when 2-chloro-4-nitroaniline is used, its production usually starts from dichlorobenzene;
Since the process of nitration and ammonolysis is long, it is expensive and difficult to obtain in high purity, so it is disadvantageous in terms of raw materials.
上記問題点を踏えて鋭意検討し、本発明の目的生成物の
一方の反応基質に、安価な２−クロロアニリン類を選択
し、これにより高収率で式（Ｉ）化合物を得、引続き特
定のニトロ化反応条件下で、出した。Based on the above-mentioned problems, we conducted extensive studies and selected inexpensive 2-chloroanilines as one of the reaction substrates for the target product of the present invention, thereby obtaining the compound of formula (I) in high yield and subsequently identifying it. It was released under the nitration reaction conditions.
すなわち、式（Ｉ）化合物を特定条件下でニトロ化した
場合、はぼ選択的にアニリド基の４位にのみニトロ基を
選択的に導入できることがわかり、本発明に達したもの
であり、本発明は式（Ｉ）人
〔式中、ＸおよびＹはそれぞれ水素原子または塩素原子
を表わす。〕
で示されるＮ−（２−クロロフェニル）−３−トリフロ
ロメチルベンゼンスルホンアミド類を、濃硫酸の存在下
または不存在下、式（Ｉ）化合物１重量部に対し０．０
５〜１０重量部の氷酢酸中、または０．０１〜２重量部
の無水酢酸中で１０〜１２０℃でニトロ化反応を行い、
式（ｎ）
λ
〔式中、Ｘ、Ｙは式（Ｉ）中のＸ、Ｙと同じである０
〕
で示されるＮ−（２−クロロ−４−ニトロフェニル）−
３−トリフロロベンゼンスルホンアミド類を得る製造方
法である。That is, it has been found that when a compound of formula (I) is nitrated under specific conditions, a nitro group can be selectively introduced only into the 4-position of the anilide group, and the present invention has been achieved. The invention relates to a compound of the formula (I) [wherein X and Y each represent a hydrogen atom or a chlorine atom]. ] 0.0 part by weight of N-(2-chlorophenyl)-3-trifluoromethylbenzenesulfonamides per 1 part by weight of the compound of formula (I) in the presence or absence of concentrated sulfuric acid.
The nitration reaction is carried out at 10 to 120°C in 5 to 10 parts by weight of glacial acetic acid or 0.01 to 2 parts by weight of acetic anhydride,
Formula (n) λ [wherein, X and Y are the same as X and Y in formula (I) 0
] N-(2-chloro-4-nitrophenyl)-
This is a manufacturing method for obtaining 3-trifluorobenzenesulfonamides.
本発明方法において、式（Ｉ）化合物から製造できる、
相応のニトロ化物である式（ｎ）化合物としては、３−
トリフロロメチルベンゼンスルホン−２−クロロ−４−
ニドロアニライド、３−トリフロロメチル−４−クロロ
−ベンゼンスルホン−２−クロロ−４−ニドロアニライ
ド、２−り四ロー５−トリフロロメチルベンゼンスルホ
ン−２−クロロ−４−ニドロアニライド、２，４−ジク
ロロ−５−トリフロロメチルベンゼンスルホン−２−ク
ロロ−４−ニドロアニライド、が挙げられる。In the method of the present invention, it can be produced from a compound of formula (I),
Corresponding nitrated compounds of formula (n) include 3-
Trifluoromethylbenzenesulfone-2-chloro-4-
Nidroanilide, 3-trifluoromethyl-4-chloro-benzenesulfone-2-chloro-4-nidroanilide, 2-trifluoro-5-trifluoromethylbenzenesulfone-2-chloro-4-nidroanilide, 2,4-dichloro- 5-trifluoromethylbenzenesulfone-2-chloro-4-nidroanilide.
また本発明に用いる式ＣＩ）化合物は、相応するベンゼ
ンスルホニルクロリド類と２−クロロアニリンの縮合に
より高収率で容易に得ることができ、ベンゼンスルホニ
ルクロリド類は、例えば、３−トリフロロメチル−４−
クロロベンゼンスルホニルクロリドは、
のように、０−トリフロロメチルクロルベンゼンにクロ
ルスルホ？酸を反応させて得ることができ、また２−ク
ロロアニリン類は公知の化合物であり安価で容易に入手
できる。Furthermore, the compounds of formula CI) used in the present invention can be easily obtained in high yields by condensation of the corresponding benzenesulfonyl chlorides with 2-chloroaniline, and the benzenesulfonyl chlorides are, for example, 3-trifluoromethyl- 4-
Chlorobenzenesulfonyl chloride is converted into 0-trifluoromethylchlorobenzene by chlorosulfonyl chloride, as in It can be obtained by reacting an acid, and 2-chloroanilines are known compounds and can be easily obtained at low cost.
本発明は、以下のようにして実施される。The present invention is carried out as follows.
Ｎ−（２−クロロフェニル）−３−トリフロロメチルベ
ンゼンスルホンアミド類の式（Ｉ）化合物１モルに対し
、０．９〜２モル、好ましくは１．０〜１．３モルの硝
酸及び弐〇）化合物１重量部に対しα０１〜２重量部、
好ましくは０．０５〜１重量部の無水酢酸、または００
５〜１０重量部、好ましくは０．０５〜５重量部の氷酢
酸を使用してニトロ化反応を行う。通常のニトロ化反応
において混酸として使用される多量の硫酸の使用は、本
発明方法では、副生物が増大するので不都合である。ま
た硝酸のみの使用では反応が遅いので、無水酢酸や氷酢
酸とともに硫酸を共存させてもよいが、その場合は式（
ｒ）化合物に対し０．１重量部以下で使用するのが良い
。また無水酢酸や氷酢酸の使用量がこれらの範囲をはず
れた場合も反応が遅くなり、異性体やジニトロ体化合物
などの副生物の生成も増加し、目的生成物の式（ｎ）化
合物の収率が低下する。0.9 to 2 mol, preferably 1.0 to 1.3 mol of nitric acid and ) α01 to 2 parts by weight per 1 part by weight of the compound,
Preferably 0.05 to 1 part by weight of acetic anhydride, or 0.05 to 1 part by weight
The nitration reaction is carried out using 5 to 10 parts by weight, preferably 0.05 to 5 parts by weight of glacial acetic acid. The use of large amounts of sulfuric acid, which is used as a mixed acid in conventional nitration reactions, is disadvantageous in the process of the present invention since by-products increase. Also, since the reaction is slow when using only nitric acid, sulfuric acid may be used together with acetic anhydride or glacial acetic acid, but in that case, the formula (
r) It is preferable to use it in an amount of 0.1 part by weight or less based on the compound. Additionally, if the amount of acetic anhydride or glacial acetic acid used is outside these ranges, the reaction will slow down, the production of by-products such as isomers and dinitro compounds will increase, and the yield of the desired product, the compound of formula (n), will decrease. rate decreases.
またその際、反応溶媒として、１，１．２−トリクロル
エタン、１，２−ジクロルエタン、四塩化炭素などを用
いるのが好ましく、その使用量は式（Ｉ）化合物１重量
部に対し、好ましくは２〜１０重量部が適当である。ま
た溶媒は全く使用しない場合でも本発明においては殆ん
ど遜色なく反応する。In this case, it is preferable to use 1,1,2-trichloroethane, 1,2-dichloroethane, carbon tetrachloride, etc. as a reaction solvent, and the amount used is preferably based on 1 part by weight of the compound of formula (I). 2 to 10 parts by weight is suitable. Furthermore, even when no solvent is used, the reaction in the present invention is almost the same.
ニトロ化反応においては、式ＣＩ）化合物、溶媒および
無水酢酸または氷酢酸を反応容器に入れ、１０〜１２０
℃、好ましくは６０〜１００℃に加熱して、硝酸を１〜
２時間で滴下装入し、その後さらに、０．５〜１０時間
撹拌して反応を終了させる。反応温度がこの範囲外であ
ると副生成物が増大するので好ましくない。In the nitration reaction, the compound of formula CI), the solvent and acetic anhydride or glacial acetic acid are placed in a reaction vessel and the
℃, preferably 60 to 100℃, and nitric acid is heated to 1 to 100℃.
The mixture is added dropwise for 2 hours, and then stirred for an additional 0.5 to 10 hours to complete the reaction. If the reaction temperature is outside this range, the amount of by-products will increase, which is not preferable.
ついで、反応液から減圧下に溶媒を留去して得られる残
ｌこ水を加え、得られた結晶をろ過、乾燥後、目的生成
物であるベンゼンスルホン−２−クロル−４°−ニトロ
アニリド類が得られる。これを必要なら、カラムクロマ
トグラフィーもしくは再結晶に付す。Next, water was added to the residue obtained by distilling the solvent off from the reaction solution under reduced pressure, and the resulting crystals were filtered and dried to obtain the desired product, benzenesulfone-2-chloro-4°-nitroanilide. can be obtained. This is subjected to column chromatography or recrystallization if necessary.
このようにして、本発明方法は、式（Ｉ）化合物のアニ
リド基の４位のみ選択的にニトロ基を導入して目的生成
物式（ｎ）化合物を得ることができる。In this manner, the method of the present invention can selectively introduce a nitro group only at the 4-position of the anilide group of the compound of formula (I) to obtain the desired product, the compound of formula (n).
また本発明においては、原料に用いる式ＣＩ）化合物は
、前記特開昭５８−２１９１５９号公報に記載された方
法に準じて有機塩基性触媒の存在下に、ベンゼンスルホ
ニルクロリドと２−クロロアニリン類の縮合反応を実施
すればよい。In the present invention, the compound of formula CI) used as a raw material is prepared by combining benzenesulfonyl chloride and 2-chloroaniline in the presence of an organic basic catalyst according to the method described in JP-A-58-219159. The condensation reaction may be carried out.
縮合反応は、塩基触媒や、必要あらばトルエンやオルソ
ジクロロベンゼンなどの溶媒を反応器に仕込み、１００
℃以上、好ましくは１３０〜１８０℃に加熱維持し、同
温度で好ましくは３〜１５時間撹拌しながら行う。その
際、発生する塩化水素を反応系外に強制的に除去するた
めに本発明においては不活性ガスを反応液中に吹き込み
ながら行うのが良い。For the condensation reaction, a base catalyst and, if necessary, a solvent such as toluene or orthodichlorobenzene are charged into a reactor, and 100%
C. or higher, preferably 130 to 180.degree. C., and preferably stirred at the same temperature for 3 to 15 hours. At this time, in order to forcibly remove generated hydrogen chloride from the reaction system, in the present invention, it is preferable to carry out the reaction while blowing an inert gas into the reaction solution.
これにより反応中副生する塩化水素は逐次有機塩基の塩
酸塩となるが、縮合反応時の温度を１３０℃以上の温度
に維持して実施すれば分解され、分解されたＨＣｌガス
は導入される不活性ガスのバブリングにより同伴されて
逐次系外に排出でき、塩基性触媒の使用量は少なくて済
み、しかも縮合工程での収率も向上する。As a result, hydrogen chloride produced as a by-product during the reaction gradually becomes hydrochloride of the organic base, but if the temperature during the condensation reaction is maintained at 130°C or higher, it will be decomposed and the decomposed HCl gas will be introduced. The inert gas can be entrained and sequentially discharged from the system by bubbling, the amount of basic catalyst used can be reduced, and the yield in the condensation step can also be improved.
次に実施例を示す。Next, examples will be shown.
実施例−１
３−トリフロロメチル−４−クロルベンゼンスルホン−
２−クロル−４−ニトロアニリドの合成（縮合工程）
５００＊／四ツ目フラスコに２−クロロアニリン２５．
５ｇ、塩基性触媒としてピリジンｌｓ、ｓｙ、 トルエ
ン１５０ゴを装入し、１１０℃に昇温し、かきまぜなが
らトルエン５０ｍ１に溶かした３−トリフロロメチル−
４−クロルベンゼンスルホニルクロライド５５．８ｇを
１００〜１１０℃で１時間を要し滴下装入した。引き続
き、同温で４時間保温かきまぜを行い、反応を終了した
。反応溶液を室温まで冷却後、５％塩酸水２００ｉ１！
を加え、３０分間かきまぜを行い分液した。Example-1 3-trifluoromethyl-4-chlorobenzenesulfone-
Synthesis of 2-chloro-4-nitroanilide (condensation step) 500*/2-chloroaniline 25.
5 g of pyridine as a basic catalyst, 150 g of toluene were charged, the temperature was raised to 110°C, and 3-trifluoromethyl-3-trifluoromethyl was dissolved in 50 ml of toluene with stirring.
55.8 g of 4-chlorobenzenesulfonyl chloride was added dropwise at 100 to 110° C. over a period of 1 hour. Subsequently, the mixture was kept warm and mixed for 4 hours at the same temperature to complete the reaction. After cooling the reaction solution to room temperature, 200 l of 5% hydrochloric acid solution was added!
was added and stirred for 30 minutes to separate the liquids.
得られた有機層を、水１００ｍ／で３回洗浄した後、減
圧下でトルエンを留去し、得られた残留物をベンゼンで
洗浄し、減圧下にろ取、乾燥して３−トリフロロメチル
−４−クロルベンゼンスルホン−２−クロル−アリニド
６７．５ｇ（収率９１．２％）を得た。The obtained organic layer was washed three times with 100ml of water, and then toluene was distilled off under reduced pressure. The obtained residue was washed with benzene, filtered under reduced pressure, and dried to obtain 3-trifluorocarbon. 67.5 g (yield 91.2%) of methyl-4-chlorobenzenesulfone-2-chloro-alinide was obtained.
また反応温度を１３０℃に維持し、窒素を反応液中に５
０ｍ１１分の流速で吹き込みながら実施した場合は、収
率が９５％であった。In addition, the reaction temperature was maintained at 130°C, and nitrogen was added to the reaction solution at 5%.
When carried out while blowing at a flow rate of 0 m11 min, the yield was 95%.
にトロ化工程）
次に、これの１８．５．９および氷酢酸５０ｄ、濃硫酸
１．０１を１００ｍＪ四ツ目フラスコに装入し、９５℃
でかきまぜながら発煙硝酸３．５ｇを氷酢酸１０ｍ１に
混合し、これを１時間を要し滴下した。Next, 18.5.9 of this, 50 d of glacial acetic acid, and 1.01 d of concentrated sulfuric acid were charged into a 100 mJ four-eye flask and heated at 95°C.
While stirring, 3.5 g of fuming nitric acid was mixed with 10 ml of glacial acetic acid, and this was added dropwise over a period of 1 hour.
さらに１００°Ｃで２時間保温かきまぜを行い反応を終
了した。冷却後、反応混合物を砕氷１００Ｊ中に排出し
、析出した結晶をろ取し、メタノール５０ｍＪで洗浄後
、乾燥を行い融点１６９．５〜１７１．５°Ｃを有し、
純度９９．７５％（ＧＣ内部標準法分析）の３−トリフ
ロロメチル−４−クロロベンゼンスルホン−２−クロロ
−４−ニトロアニリド１８．３ｇ（収率８８．９％）を
得た。The mixture was further heated and stirred at 100°C for 2 hours to complete the reaction. After cooling, the reaction mixture was discharged into 100 J of crushed ice, and the precipitated crystals were collected by filtration, washed with 50 mJ of methanol, and dried.
18.3 g (yield: 88.9%) of 3-trifluoromethyl-4-chlorobenzenesulfone-2-chloro-4-nitroanilide with a purity of 99.75% (GC internal standard method analysis) was obtained.
実施例−２
２−クロル−５−トリフロロメチルベンゼンスルホン−
２−クロル−４−ニトロアニリドの合成実施例−１の縮
合工程で、３−トリフロロメチル−４−クロルベンゼン
スルホニルクロライドを用いた代りに、３−トリフロロ
メチル−６−クロルベンゼンスルホニルクロライドを用
いた以外は全く同様にして得られた３−トリ２０口メチ
ル−６−クロルベンゼンスルホン−２−クロルアニリド
１８．５ｇ、無水酢酸１．０．９および溶媒の１，１゜
２−トリクロルエタン５０ｍＪを２００ｍＪ四ツロフラ
スコに装入し、９５℃に昇温し、かきまぜつつ１５ｍ１
の１，１．２−トリクロルエタンに溶解した発煙硝酸３
．５ｇを、１時間を要し９４〜９６°Ｃで滴下装入した
。引き続き、同温で２時間保温かきまぜを行い、反応を
終了させ、室温まで冷却した。得られた反応混合物を減
圧下で溶媒を留去し残留物を、水１００ゴで洗浄後、ろ
取した。粗結晶をメタノール５０ｍＪで洗浄した後、乾
燥し、３−トリフロロメチル−６−クロルベンゼンスル
ホンー２−クロロ−４−ニトロアニリド（融点１５７、
５〜１５＆５°Ｇ） １７．５９ （収率８４．３％）
を得た。Example-2 2-chloro-5-trifluoromethylbenzenesulfone-
Synthesis of 2-chloro-4-nitroanilide In the condensation step of Example 1, 3-trifluoromethyl-6-chlorobenzenesulfonyl chloride was used instead of 3-trifluoromethyl-4-chlorobenzenesulfonyl chloride. 18.5 g of 3-tri20 methyl-6-chlorobenzenesulfone-2-chloroanilide obtained in exactly the same manner except that 1.0.9 g of acetic anhydride and 1,1° 2-trichloroethane as a solvent were used. Charge 50mJ into a 200mJ four-way flask, raise the temperature to 95℃, and add 15ml while stirring.
Fuming nitric acid 3 dissolved in 1,1,2-trichloroethane of
．． 5 g was added dropwise over a period of 1 hour at 94-96°C. Subsequently, the mixture was kept warm and stirred at the same temperature for 2 hours to complete the reaction, and the mixture was cooled to room temperature. The solvent of the resulting reaction mixture was distilled off under reduced pressure, and the residue was washed with 100 g of water and collected by filtration. The crude crystals were washed with 50 mJ of methanol and then dried to give 3-trifluoromethyl-6-chlorobenzenesulfone-2-chloro-4-nitroanilide (melting point 157,
5-15&5°G) 17.59 (yield 84.3%)
I got it.
実施例−３
３−トリフロロメチルベンゼンスルホン−２−クロル−
４−ニトロアニリドの合成
実施例−１の縮合工程と全く同様にして得られた３−ト
リフロロメチルベンゼンスルホン−２−クロルアニライ
ド１６．８９、触媒の無水酢酸０．３ｇ、１，１，２−
トリクロルエタン４０ｍ／の混合物を９５℃に昇温させ
、同温にて９８％−硝酸３．５ｇを含む１，１．２−ト
リクロルエタン１０ｍ１の溶液を１時間を要して滴下し
た。その後９０〜゛９５°Ｃで１時間保温かきまぜ、反
応を終了した。Example-3 3-trifluoromethylbenzenesulfone-2-chloro-
Synthesis of 4-nitroanilide 16.89 g of 3-trifluoromethylbenzenesulfone-2-chloroanilide obtained in exactly the same manner as the condensation step of Example 1, 0.3 g of acetic anhydride as a catalyst, 1,1, 2-
A mixture of 40 m/ml of trichloroethane was heated to 95°C, and at the same temperature, a solution of 10 ml of 1,1,2-trichloroethane containing 3.5 g of 98% nitric acid was added dropwise over 1 hour. Thereafter, the mixture was kept warm at 90 to 95°C for 1 hour to complete the reaction.
反応液を冷却後、減圧下に溶媒を留去し、残留物を水１
００ｍＡ’に注加し結晶化させ、ろ別した。After cooling the reaction solution, the solvent was distilled off under reduced pressure, and the residue was dissolved in water 1
00 mA' to crystallize, and filtered.
結晶を水１００ゴで水洗、乾燥後、メタノール４ＱｍＡ
’を用い再結晶を行い、３−トリフロロメチルベンゼン
スルホン−２−クロル−４−ニトロアニリド（融点１２
６〜１２７℃）１３．２９（収率６９．３％）を得た。Wash the crystals with 100 g of water, dry, and add 4 QmA of methanol.
' 3-trifluoromethylbenzenesulfone-2-chloro-4-nitroanilide (melting point 12
6-127°C) 13.29 (yield 69.3%) was obtained.
参考例
４００ｍＡ！フラスコ内にオルソジクロロベンゼン２０
０ｍ７！、ピリジンｌ＋ｎＡ！および２−りＤＯ−４−
ニトロアニリン１．７９ （０，０１モル）を装入し、
かきまぜながら３−トリフルオロメチルベンゼンスルホ
クロリド２．５ ｇ（０，０１モル）を室温で３０分を
要して滴下した。その後加温し還流下（Ｉ７５〜１８０
°Ｃ）に１０時間かきまぜて、反応を終えた。Reference example 400mA! 20 orthodichlorobenzene in the flask
0m7! , pyridine l+nA! and 2-riDO-4-
1.79 (0.01 mol) of nitroaniline was charged,
While stirring, 2.5 g (0.01 mol) of 3-trifluoromethylbenzenesulfochloride was added dropwise at room temperature over 30 minutes. Thereafter, it was heated under reflux (I75-180
℃) for 10 hours to complete the reaction.
室温まで冷却後、反応液を希塩酸ついで水で十分洗浄し
、無水硫酸ナトリウムで脱水後、減圧下にオルソジクロ
ロベンゼンを留去した。その残分を実施例−３に準じて
精製し、３−トリフロロメチルベンゼンスルホン−２−
クロル−４−ニトロアニリド１．９．９（収率５０％）
を得た。After cooling to room temperature, the reaction solution was thoroughly washed with diluted hydrochloric acid and then water, dried over anhydrous sodium sulfate, and then orthodichlorobenzene was distilled off under reduced pressure. The residue was purified according to Example 3, and 3-trifluoromethylbenzenesulfone-2-
Chlor-4-nitroanilide 1.9.9 (yield 50%)
I got it.
Claims (1)
を表わす。〕 で示されるＮ−（２−クロロフェニル）−３−トリフロ
ロメチルベンゼンスルホンアミド類を、濃硫酸の存在下
または不存在下、式（ I ）化合物１重量部に対し０．
０１〜２重量部の無水酢酸中、１０〜１２０℃でニトロ
化反応を行う、式（II） ▲数式、化学式、表等があります▼（II） 〔式中、Ｘ、Ｙは式（ I ）中のＸ、Ｙと同じである。
〕 で示されるＮ−（２−クロロ−４−ニトロフェニル）−
３−トリフロロメチルベンゼンスルホンアミド類の製造
方法。 ２ 式（ I ） ▲数式、化学式、表等があります▼（ I ） 〔式中、ＸおよびＹはそれぞれ水素原子または塩素原子
を表わす。〕 で示されるＮ−（２−クロロフェニル）−３−トリフロ
ロメチルベンゼンスルホンアミド類を、濃硫酸の存在下
または不存在下、式（ I ）化合物１重量部に対し０．
０５〜１０重量部の氷酢酸中、１０〜１２０℃でニトロ
化反応を行う、式（II） ▲数式、化学式、表等があります▼（II） 〔式中、Ｘ、Ｙは式（ I ）中のＸ、Ｙと同じである。
〕 で示されるＮ−（２−クロロ−４−ニトロフェニル）−
３−トリフロロメチルベンゼンスルホンアミド類の製造
方法。 （３）濃硫酸を、式（ I ）化合物１重量部に対し、０
〜０．１重量部存在させる特許請求の範囲第１項または
第２項記載の方法。[Claims] 1 Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X and Y each represent a hydrogen atom or a chlorine atom. ] N-(2-chlorophenyl)-3-trifluoromethylbenzenesulfonamide represented by the formula (I) in the presence or absence of concentrated sulfuric acid in an amount of 0.0% per 1 part by weight of the compound of formula (I).
A nitration reaction is carried out at 10 to 120°C in 01 to 2 parts by weight of acetic anhydride. Formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [In the formula, Same as X and Y inside.
] N-(2-chloro-4-nitrophenyl)-
A method for producing 3-trifluoromethylbenzenesulfonamides. 2 Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X and Y each represent a hydrogen atom or a chlorine atom. ] N-(2-chlorophenyl)-3-trifluoromethylbenzenesulfonamide represented by the formula (I) in the presence or absence of concentrated sulfuric acid in an amount of 0.0% per 1 part by weight of the compound of formula (I).
A nitration reaction is carried out at 10 to 120°C in 05 to 10 parts by weight of glacial acetic acid. Formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [In the formula, X and Y are formula (I) Same as X and Y inside.
] N-(2-chloro-4-nitrophenyl)-
A method for producing 3-trifluoromethylbenzenesulfonamides. (3) Add 0 concentrated sulfuric acid to 1 part by weight of the compound of formula (I).
3. A method according to claim 1 or claim 2, wherein ~0.1 part by weight is present.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20799086A JPH0733367B2 (en) | 1986-09-05 | 1986-09-05 | Process for producing N- (2-chloro-4-nitrophenyl) -3-trifluoromethylbenzenesulfonamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20799086A JPH0733367B2 (en) | 1986-09-05 | 1986-09-05 | Process for producing N- (2-chloro-4-nitrophenyl) -3-trifluoromethylbenzenesulfonamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6363652A true JPS6363652A (en) | 1988-03-22 |
| JPH0733367B2 JPH0733367B2 (en) | 1995-04-12 |
Family
ID=16548852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20799086A Expired - Fee Related JPH0733367B2 (en) | 1986-09-05 | 1986-09-05 | Process for producing N- (2-chloro-4-nitrophenyl) -3-trifluoromethylbenzenesulfonamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733367B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491924A (en) * | 2011-12-14 | 2012-06-13 | 天津市筠凯化工科技有限公司 | Preparation method for N-(2- chlorine-4-phenyl)-4- chlorine-3-trifluoromethyl benzene sulfonamide |
-
1986
- 1986-09-05 JP JP20799086A patent/JPH0733367B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491924A (en) * | 2011-12-14 | 2012-06-13 | 天津市筠凯化工科技有限公司 | Preparation method for N-(2- chlorine-4-phenyl)-4- chlorine-3-trifluoromethyl benzene sulfonamide |
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| Publication number | Publication date |
|---|---|
| JPH0733367B2 (en) | 1995-04-12 |
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